CN106744730A - Gallium oxide, gallium nitride nano-powder are prepared by raw material two-step method of gallium - Google Patents
Gallium oxide, gallium nitride nano-powder are prepared by raw material two-step method of gallium Download PDFInfo
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Abstract
Gallium oxide, gallium nitride nano-powder are prepared by raw material two-step method of gallium, reacted at 180-280 DEG C, in autoclave using the ratio of metal Ga and water in mass ratio 1: 2-10 and obtain gallium oxide hydroxide, then heat resolve gallium oxide hydroxide can obtain the gallium oxide nano-powder that particle diameter is 10-20nm in air at a temperature of 400 DEG C -800 DEG C, high-quality gallium nitride nanometer powder can obtain in 2-4 hours with ammonia nitridation gallium oxide hydroxide again, and particle diameter is in 20~30nm.The method have easy, economic, environmental protection, can prepare with scale high-quality gallium oxide, the good effect of gallium nitride nano-powder.
Description
Technical field
The present invention relates to a kind of method for preparing high-quality gallium oxide, gallium nitride nano-powder.
Background technology
Gallium nitride (GaN) is a kind of direct band gap semiconductor material with wide forbidden band, in photoelectron and microelectronics
The aspects such as device have extensive use.At present its research with application turned into global semiconductor study forward position and
Focus.A large amount of preparations of GaN powders can be its socialization extensively using compacting material base.From 1932
(J.Phys.Chem.1932,36,2651), research work since Johnson et al. research GaN powder synthesis
Preparation of the person to GaN powders has been carried out a large amount of in-depth studies.Current people typically use solid phase method, liquid
Phase method and vapor phase method three kinds of methods obtain substantial amounts of GaN powders.Some general gallium base predecessors are essentially
Gallium oxide, gallium chloride or the organic compound containing gallium, these gallium substratess matter are most costly, quick to air
Sense even severe toxicity, these unfavorable factors can cause the cost for synthesizing GaN to increase, and right in preparation process
Synthesis device proposes high requirement；Not only in this, the GaN powders that these methods synthesize can also be because of forerunner
Inevitably it is contaminated using to a large amount of catalyst in impurity element present in thing or course of reaction,
It is impure that this also results in synthetic product.(J.Electrochem.Soc.1961,108,1072；J.Electrochem.
Soc.1962,109,24；J.Mater.Sci.1992,27,2580；J.Am.Ceram.Soc.1996,79,2309；
Appl.Phys.Lett.1996,69,1285；Chem.Mater.1999,11,2299；J.Mater.Res.2000,
15,974；J.Phys.Chem.B 2001,105,11922；Phys.Stat.Sol.2005,2,2074；Chem.
Mater., 2007,19,3499；CrystEngComm 2014,16,3584.).So, substantial amounts of gan powder
If with ammonia or nitrogen, Direct-Nitridation metal Ga is obtained at relatively high temperatures, and this will most easy most be passed through
The path of Ji.But metal Ga temperature be higher than 30 DEG C when often due to itself very big surface tension and with
Big drops are present, although being nitrogenized so at a high temperature of higher than 1000 DEG C, N atoms are hardly entered.
Therefore, up to the present also rarely have on largely preparing GaN nano-powders by Direct-Nitridation metal Ga
Report.
Gallium oxide (Ga2O3) it is a kind of excellent chemistry, the wide band gap semiconducter of heat endurance, its nanometer
Powder is even more a kind of excellent photochemical catalyst, be widely used in light decomposition water, carbon dioxide extinguisher reduction and
(Catal.Lett.2008,125,22-26 in wastewater treatment；Chem.Phys.Lett.2008,467,191-194；
Environ.Sci.Technol.2006,40,5799-5803.) past people use wet chemical method mostly, with gallium
Based compound synthesizes gallium oxide nano-powder (Arab.J.Chem.2009,2,73-77 for raw material；Mater.Lett.
2005,59,1227-1233.).Undoubtedly, the impurity element that predecessor gallium based compounds contain can be to last oxidation
Gallium material produces influence.So directed oxidation metal gallium synthesis gallium oxide will be most easy most pure path,
But this technology path equally faces foregoing problem：Gallium is low-melting-point metal, can be coagulated after fusing
Big drop is polymerized to, oxygen atom is difficult a large amount of dissolvings wherein.Equally, also rarely have on by direct oxidation at present
Metal Ga largely prepares Ga2O3The report of nano-powder
In the report reported before us, with soluble-salt sodium sulphate as dispersant, by after grinding,
Enable that metal Ga is more evenly distributed in the surface of soluble-salt, it is then fully oxidized in tube furnace
Or nitridation metal Ga and Na2SO4Mixture after, metal Ga can be completely converted into Ga2O3Or GaN, then
By distilled water flushing, you can pure nanoscale Ga is obtained2O3Nanocrystalline with GaN (Appl.Phys.A, 2014,
114,351-356；CrystEngComm 2010,12,2037-2039.).But due to the soluble-salt for using
Na2SO4Molten, boiling point it is relatively low (fusing point is less than 850 DEG C, while decomposing), which limits nitridation temperature
Degree is not above more than 800 DEG C, so the crystallinity quality of the gallium based material for finally obtaining is not high, also just limits
The range of application of product.The present invention uses two-step method, with gallium as raw material, first allows gallium and water to steam
Solid/liquid/gas reactions obtain gallium oxide hydroxide, and hydroxyl oxidation is then calcined or nitrogenized under Muffle furnace or tube furnace high temperature
Gallium, just can largely obtain Ga2O3Or GaN nano-powders.Because the experimental implementation only needs to very simple height
Pressure reaction kettle device, calcines or in the nitridation of thermal chemical vapor deposition system high temperature, institute in Muffle furnace high temperature
With the high-quality of large-scale production as required Ga that can be very easy2O3Or GaN nano-powders.
The content of the invention
It is an object of the invention to provide one kind with gallium be Material synthesis high-quality Ga2O3With GaN nano powders
The approach of body.
The present invention is solved by following technical proposal：Opened with a certain amount of moisture using metal Ga
Put in autoclave, then obtain gallium oxide hydroxide in 180-280 DEG C of reaction；At 400 DEG C -800 DEG C
Calcined 2-4 hours in Muffle furnace, natural cooling can obtain high-purity gallium oxide nano-powder；800 DEG C-
Gallium oxide hydroxide is nitrogenized 2-4 hours with ammonia in 1000 DEG C of tube furnace, after natural cooling, you can obtain height
Pure, high-quality gallium nitride nanometer powder.
Brief description of the drawings
Fig. 1 is reacted with 2 grams of galliums and 5 milliliters of water in autoclave, and reaction temperature is 180-
280 DEG C, the reaction time is 5 hours, obtains the intermediate product gallium oxide hydroxide of white.
Fig. 2 X-ray diffractograms, show that the intermediate product is gallium oxide hydroxide.
Fig. 3 X-ray diffractograms and transmission electron microscope picture, show that calcining gallium oxide hydroxide can in Muffle furnace
Gallium oxide material is obtained, and particle diameter is in 10-20nm.
Fig. 4 X-ray diffractions and Raman spectrum lab diagram and infrared spectrogram, show that the product is six sides
Phase GaN, and nitriding temperature is higher, the product crystallinity for obtaining is also higher；The outward appearance picture of product shows simultaneously
Show that the product that 800 DEG C of nitridation gallium oxide hydroxides are obtained is faint yellow, the product that 900 DEG C of nitridation gallium oxide hydroxides are obtained
Thing is yellow, and the product that 1000 DEG C of nitridation gallium oxide hydroxides are obtained is glassy yellow.
Fig. 5：Transmission electron microscope (TEM) and high resolution electron microscopy (HRTEM) figure, show that gan powder is
It is made up of nanometer particle, and nitriding temperature is higher, the product crystallinity for obtaining is also higher；In 1000 DEG C of temperature
Degree nitrogenizes down the nanocrystalline size of the product for obtaining in~30nm, and the lattice fringe of particle is high-visible, explanation
The crystallinity of product is very high.X-ray energy scattering spectra (EDX) show product be rich in gallium type compound,
And nitriding temperature is higher, nitrogen is also higher with the atomic ratio of gallium.
Specific embodiment
Embodiment 1
Reacted in autoclave with 2 grams of galliums and 5 milliliters of water, reaction temperature is 250 DEG C, reaction
Time is 5 hours, obtains the intermediate product gallium oxide hydroxide of white.Then respectively at 400 DEG C in Muffle furnace
With 800 DEG C at calcine gallium oxide hydroxide 2 hours, you can obtain α-or beta-gallium oxide white powder.Product
Characterize as shown in Figures 2 and 3.
Embodiment 2
Reacted in autoclave with 2 grams of galliums and 5 milliliters of water, reaction temperature is 250 DEG C, reaction
Time is 5 hours, obtains the intermediate product gallium oxide hydroxide of white.Then in the tube furnace at 800 DEG C with ammonia
Gas nitridation gallium oxide hydroxide 3 hours, you can obtain flaxen gan powder.Product is named as GaN 800,
The sign of product is as shown in Fig. 2, Fig. 4 and Fig. 5.
Embodiment 3
Reacted in autoclave with gallium and water, reaction temperature is 250 DEG C, and the reaction time is 5
Hour, obtain the intermediate product gallium oxide hydroxide of white.Then hydroxyl is nitrogenized with ammonia at 900 DEG C in the tube furnace
Base gallium oxide 3 hours, you can obtain the gan powder of yellow.Product is named as GaN 900, the table of product
Levy as shown in Fig. 2, Fig. 4 and Fig. 5.
Embodiment 4
Reacted in autoclave with gallium and water, reaction temperature is 250 DEG C, and the reaction time is 5
Hour, obtain the intermediate product gallium oxide hydroxide of white.Then nitrogenized with ammonia at 1000 DEG C in the tube furnace
Gallium oxide hydroxide 3 hours, you can obtain the gan powder of glassy yellow.Product is named as GaN 1000, product
Sign as shown in Fig. 2, Fig. 4 and Fig. 5.
Claims (4)
1. gallium oxide, gallium nitride nano-powder are prepared by raw material two-step method of gallium, it is characterized in that with metal
Gallium is gallium source, separated in autoclave with water as oxidant, then at 180~280 DEG C
Reaction obtains gallium oxide hydroxide.
2. it is according to claim 1 to prepare gallium oxide, gallium nitride nanometer by raw material two-step method of gallium
Powder, it is characterized in that calcining gallium oxide hydroxide in 400~800 DEG C in Muffle furnace, institute is obtained with this
The gallium oxide nano-powder for needing.
3. it is according to claim 1 to prepare gallium oxide, gallium nitride nanometer by raw material two-step method of gallium
Powder, it is characterized in that small in 800~1000 DEG C of nitridation gallium oxide hydroxides three in tube furnace ammonia atmosphere
When.
4. it is according to claim 1 to prepare gallium oxide, gallium nitride nanometer by raw material two-step method of gallium
Powder, it is characterized in that being calcined in Muffle furnace through naturally cooling to room temperature, then obtains the oxygen of white
Change gallium nano-powder；Room temperature is naturally cooled in tube furnace ammonia, the nitridation of yellow then can be obtained
Gallium nano-powder.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089646A (en) * | 2017-06-20 | 2017-08-25 | 陕西师范大学 | A kind of preparation method of GaN nano particles |
| CN107670684A (en) * | 2017-10-27 | 2018-02-09 | 张香丽 | A kind of embedded type TiO2Hollow ball/GaN/Ga2O3Heterojunction photocatalysis film and preparation method thereof |
| CN107935027A (en) * | 2017-11-27 | 2018-04-20 | 三峡大学 | A kind of new type lithium ion battery negative active core-shell material a GaOOH and preparation method |
| CN110627112A (en) * | 2019-10-12 | 2019-12-31 | 成都中建材光电材料有限公司 | Preparation method and preparation device of high-purity gallium oxide |
| CN112850664A (en) * | 2021-01-26 | 2021-05-28 | 西安理工大学 | Preparation method of gallium nitride nanosheet |
| CN115101636A (en) * | 2022-08-24 | 2022-09-23 | 江苏第三代半导体研究院有限公司 | Composite micro-nano semiconductor structure, preparation method and application thereof |
| CN115974133A (en) * | 2022-12-26 | 2023-04-18 | 株洲科能新材料股份有限公司 | High-purity beta gallium oxide nano-microspheres and preparation method thereof |
| CN116199251A (en) * | 2023-02-03 | 2023-06-02 | 安徽工业大学 | Method for efficiently preparing gallium oxyhydroxide |
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2015
- 2015-11-19 CN CN201510835364.6A patent/CN106744730A/en active Pending
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| HONG-DI XIAO ET AL.: "Synthesis and structural properties of GaN particles from GaO2H powders", 《DIAMOND & RELATED MATERIALS》 * |
| VIJAY BHOOSHAN KUMAR ET AL.: "Facile synthesis of gallium oxide hydroxide by ultrasonic irradiation of molten gallium in water", 《ULTRASONICS SONOCHEMISTRY》 * |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089646A (en) * | 2017-06-20 | 2017-08-25 | 陕西师范大学 | A kind of preparation method of GaN nano particles |
| CN107089646B (en) * | 2017-06-20 | 2019-06-28 | 陕西师范大学 | A kind of preparation method of GaN nano particle |
| CN107670684A (en) * | 2017-10-27 | 2018-02-09 | 张香丽 | A kind of embedded type TiO2Hollow ball/GaN/Ga2O3Heterojunction photocatalysis film and preparation method thereof |
| CN107670684B (en) * | 2017-10-27 | 2020-06-02 | 张香丽 | Embedded TiO2Hollow sphere/GaN/Ga2O3Heterojunction photocatalytic film and preparation method thereof |
| CN107935027A (en) * | 2017-11-27 | 2018-04-20 | 三峡大学 | A kind of new type lithium ion battery negative active core-shell material a GaOOH and preparation method |
| CN110627112A (en) * | 2019-10-12 | 2019-12-31 | 成都中建材光电材料有限公司 | Preparation method and preparation device of high-purity gallium oxide |
| CN112850664A (en) * | 2021-01-26 | 2021-05-28 | 西安理工大学 | Preparation method of gallium nitride nanosheet |
| CN115101636A (en) * | 2022-08-24 | 2022-09-23 | 江苏第三代半导体研究院有限公司 | Composite micro-nano semiconductor structure, preparation method and application thereof |
| CN115101636B (en) * | 2022-08-24 | 2022-12-02 | 江苏第三代半导体研究院有限公司 | Composite micro-nano semiconductor powder structure, preparation method and application thereof |
| CN115974133A (en) * | 2022-12-26 | 2023-04-18 | 株洲科能新材料股份有限公司 | High-purity beta gallium oxide nano-microspheres and preparation method thereof |
| CN116199251A (en) * | 2023-02-03 | 2023-06-02 | 安徽工业大学 | Method for efficiently preparing gallium oxyhydroxide |
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